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Human exposure to per- and polyfluoroalkyl substances (PFASs) continues to be a concern. Little is known about their toxicokinetics, particularly with regard to fecal excretion of PFASs. Because pets are sentinels of human exposure to environmental contaminants, analysis of PFASs in pet feces can provide information about rates of excretion of these chemicals. In this study, 15 PFASs were measured in cat and dog feces collected from the Albany area of New York State. All PFASs except perfluorodecanesulfonate and perfluoroheptanoic acid were found in cat and dog feces. The sum concentrations of 13 PFASs (∑PFAS) varied between 21.6 and 474 (mean: 85.4 ± 94.5) ng/g dry weight for dogs, which were slightly higher than those found for cats (range: 18.0–165 ng/g dry weight, mean: 54.7 ± 26.9 ng/g dry weight). Long-chain perfluorocarboxylic acids with 9–12 carbons (perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid) were predominant in pet feces. Perfluorooctan...

Previous studies suggested immunotoxicity of perfluoroalkyl substances (PFASs), but contradictory findings were reported for the associations of PFASs with allergies. The current study aimed to investigate the association of serum PFASs with incident chronic spontaneous urticaria (CSU) in adults. A nested case-control study within a longitudinal cohort of 7051 government employees in China was conducted. Participants with urticaria at the baseline were excluded. During the first follow-up, 70 incident CSU cases were included, and 70 matched healthy controls were randomly selected. In serum samples collected at the baseline, eight PFASs were determined using the UHPLC-MS/MS approach. The median serum concentrations of perfluorobutanoic acid (PFBA) and perfluoroheptanoic acid (PFHpA) were significantly higher in participants with incident CSU. The area under the receiver operating characteristic curve was 0.714 (95% CI: 0.60–0.83) based on the joint prediction by PFBA and PFHpA. The Bayesian kernel machine regression showed a nonlinear positive overall effect of the mixture of PFASs, and identified significant single effects of PFBA and PFHpA. Serum interleukin-4 was significantly higher in the case group at baseline, and was positively associated with PFHpA (r = 0.24). Causal mediation analysis indicated interleukin-4 as a partial mediator (14.8%) in the association of PFHpA with CSU. In conclusion, serum PFASs are associated with an increased risk of incident CSU, and PFBA and PFHpA might be the effective compounds.

Perfluoroalkyl acids (PFAAs) are a form of toxic pollutant that can be transported across the globe and accumulated in the bodies of wildlife and humans. A nationwide geographical investigation considering atmospheric PFAAs via a passive air sampler (PAS) based on XAD (a styrene–divinylbenzene copolymer) was conducted in 23 different provinces/municipalities/autonomous regions in China, which provides an excellent chance to investigate their occurrences, spatial trends, and potential sources. The total atmospheric concentrations of 13 PFAAs (n=268) were 6.19–292.57 pg m−3, with an average value of 39.84±28.08 pg m−3, which were higher than other urban levels but lower than point source measurements. Perfluorooctanoic acid (PFOA) was the dominant PFAA (20.6 %), followed by perfluorohexanoic acid (PFHxA), perfluorooctane sulfonate (PFOS), and perfluoroheptanoic acid (PFPeA). An increasing seasonal trend of PFAA concentrations was shown as summer < autumn < spring < winter, which may be initiated by stagnant meteorological conditions. Spatially, the content of PFAAs displayed a declining gradient trend of central China > northern China > eastern China > north-eastern China > south-western China > north-western China > southern China, and Henan contributed the largest proportion of PFAAs. Four sources of PFAAs were identified using a positive matrix factorization (PMF) model, including PFOS-based products (26.1 %), products based on PFOA and perfluorononanoic acid (PFNA; 36.6 %), degradation products of fluorotelomer-based products (15.5 %), and an unknown source (21.8 %).

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) draw considerable attention for their potential toxic effects in humans and environment. Drinking water is accepted as one of the major exposure pathways for PFASs. In this study, we measured concentrations of 10 perfluoroalkyl substances in 94 tap water samples collected in two different sampling periods (August 2017 and February 2018) from 33 provinces of Turkey, as well as in 26 different brands of plastic and glass-bottled water samples sold in supermarkets in Turkey. Perfluorohexanoic acid (PFHxA), perfluorobutane sulfonate (PFBS) and perfluoropentanoic acid (PFPeA) were the most frequently detected PFASs in the samples of tap waters. The maximum concentrations in tap waters were measured as 2.90, 2.37, 2.18, 2.04, and 1.93 ng/L, for PFHxA, perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), and perfluorobutanoic acid (PFBA), respectively. The most abundant perfluorinated chemical in tap water samples was PFBA with 17%, followed by PFOS (13%), PFBS (12%), perfluoroheptanoic acid (PFHpA) (11%), PFHxA (11%), and PFOA (11%). The total PFASs concentration in tap water ranged from 0.08 to 11.27 ng/L. As regards bottled waters, the concentrations of PFASs were generally lower than those in tap water samples. These results revealed that tap water samples in Turkey might be considered generally safe based on the established guidelines around the world. However, due to their persistence and potential to accumulate and reach higher concentrations in the environment, careful monitoring of PFASs in all types of water is critical. (C) 2019 Elsevier Ltd. All rights reserved.

Concentrations of poly- and perfluorinated substances (PFASs) were determined in Hartbeespoort and Roodeplaat Dams, South Africa. Water samples were collected from the dams in February–March, and May–June, representing southern hemisphere summer and winter seasons, respectively. Solid phase extraction (SPE) was used to extract the analytes from the water samples and liquid chromatography-tandem mass spectrometry (LC-MS/MS) used for analysis. The mean PFAS concentrations detected ranged from 1.38–346.32 ng∙L-1 and 2.31–262.29 ng∙L-1 in the Hartbeespoort Dam and Roodeplaat Dam, respectively. Perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorohexane sulfonic acid (PFHxS) and perfluoroheptanoic acid (PFHpA) were the most dominant PFASs detected. The PFAS concentrations detected were higher in summer than in winter, but the difference between seasons was not statistically significant (p = 1). Furthermore, the concentrations of short-chain PFASs were higher than the longer chains. Overall, the PFAS concentrations in the present study are comparable to those reported in other parts of South Africa, and also Ghana, higher than the concentrations reported in Uganda, Singapore, and Vietnam, and lower than those in Germany, Japan and China. The measured concentrations of PFOA and PFOS raise concerns of human exposure to these chemicals since they are above the USEPA advisory limit. This suggests that communities living within the vicinity of the dams are most likely to be exposed to these chemicals.

Consumption of fish is one of the predominant sources of human exposure to per- and polyfluoroalkyl substances (PFASs). In this study, the effect of various cooking methods (boiling, steaming, grilling and frying) on the levels of PFASs in fish muscle and the intake of PFASs was explored by using grass carp collected from Tangxun Lake, Wuhan, China. Perfluorooctane sulfonate (PFOS) was the predominant PFASs in raw fish fillets, with the concentrations ranging from 59.6 to 136 ng/g ww, followed by perfluorobutane sulfonate (PFBS) (7.73–51.9 ng/g ww). The concentrations of long-chain PFASs in fish increased after cooking, while those of short-chain PFASs decreased. The amounts of PFASs in the cooked fish fillets decreased except PFOS. Short-chain PFASs, including PFBS and perfluoroheptanoic acid (PFHpA), were dominant in cooking juice. The highest amounts of PFBS in the juices were observed after boiling and frying, even higher than those in cooked fish fillets, suggesting that the release of short-chain PFASs to the cooking juices could not be neglected. Based on these results, the intake of short-chain PFASs amount through cooked fish fillets slightly decreased, but the intake of PFOS amount increased. However, consumption of cooking juice (fish soup) could increase the exposure risk of PFBS. Comprehensively considering the increase of PFOS and decrease of total PFASs, boiling may be the relatively better method to cook fish. As PFASs are ubiquitous and inevitable in aquatic food, it is thus important to choose appropriate cooking processes and dietary habits for reducing the intake of different PFASs from fish.

The present study focuses on the determination of the occurrence and levels of per- and polyfluoroalkyl substances (PFASs) in the drinking and source water from the Philippines and Thailand. A total of 46 samples (18 commercial bottled waters, 5 drinking water from vending machine (re-fill stations) and 23 source water) were analyzed using liquid chromatography with tandem high-resolution mass spectrometry. Using the targeted method, 12 different PFASs were detected in the drinking water samples with total quantifiable PFASs (∑PFASs) levels ranging from 7.16 to 59.49 ng/L; 15 PFASs were detected in source water with ∑PFASs ranging from 15.55 to 65.65 ng/L. A 100% detection frequency was observed for perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorosulfonic acid (PFOS) in all water samples. Six other PFASs, not included in the targeted analysis, were detected using the suspect screening approach. For the first time, the presence of 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA) in drinking water is reported, and 3 novel PFASs (C5H5OF8, C6H4O2F6, and C9H2O2F16) were detected using suspect screening in source water. Combined results from target and suspect screening analysis showed that PFASs detected were predominantly (52%) short-chain (with fluorinated alkyl chain of ≤6) which could be explained by their high mobility in the environment. The detected PFASs levels in drinking water will not likely pose immediate health risk to consumers according to US EPA health advisory for PFOS and PFOA of 70 ng/L, but inclusion of bottled and drinking water from re-fill stations in monitoring programs is warranted.

Per- and polyfluoroalkyl substances (PFASs), with their water- and heat-resistant properties, have been widely used in industrial and consumer products, including floor waxes. Adverse health effects are associated with PFAS exposures (e.g., increased risk of cancer and immunotoxicity); however, exposures resulting from the use of PFAS-containing products are poorly understood. This study examines PFAS emissions during professional floor stripping/waxing and their potential for occupational exposures. We measured PFASs in dust and airborne particulate matter (PM2.0, aerodynamic diameter ≤2.0 μm) before, during, and after floor stripping/waxing activities in three rooms in a university building. PM2.0 samples were analyzed for 34 targeted PFASs by ultra-high performance liquid chromatography coupled to electrospray ionization triple quadrupole mass spectrometer (UHPLC/ESI-MS/MS). In total, ten PFASs were detected in PM2.0 collected during floor stripping/waxing. Five were consistently higher during floor stripping/waxing compared to before (two with 95% confidence interval): perfluoro-2-methoxyacetic acid, perfluorobutanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, and perfluorooctane sulfonic acid. For these five, estimated exposures during floor stripping were 80.6, 320.5, 83.8, 29.6, and 157.7 pg m−3 per hour of floor stripping, respectively, one order of magnitude greater than typical residential indoor and two orders of magnitude greater than ambient outdoor concentrations. Estimated emission rates were 3.0, 9.6, 3.4, 1.5, and 6.5 ng h−1m−2, respectively (34.6% uncertainty). Inhalation occupational exposures were in the range of 9.42–23.2 pg per kg body weight per hour of floor stripping across the five PFASs.

With the phasing out of long-chain per- and polyfluoroalkyl substances (PFASs), production of a wide variety of alternative PFASs has increased to meet market demand. However, little is known about the bioaccumulation potential of these replacement compounds. Here, we developed a modeling workflow that combines molecular docking and molecular dynamics simulation techniques to estimate the relative binding affinity of a total of 15 legacy and replacement PFASs for human and rat liver-type fatty acid binding protein (hLFABP and rLFABP). The predicted results were compared with experimental data extracted from three different studies. There was good correlation between predicted free energies of binding and measured binding affinities, with correlation coefficients of 0.97, 0.79, and 0.96, respectively. With respect to replacement PFASs, our results suggest that EEA and ADONA are at least as strongly bound to rLFABP as perfluoroheptanoic acid (PFHpA), and as strongly bound to hLFABP as perfluorooctanoic acid (PFOA). For F-53 and F-53B, both have similar or stronger binding affinities than perfluorooctanesulfonate (PFOS). Given that interactions of PFASs with proteins (e.g., LFABPs) are important determinants of bioaccumulation potential in organisms, these alternatives could be as bioaccumulative as legacy PFASs, and are therefore not necessarily safer alternatives to long-chain PFASs.

We examined associations between prenatal exposure to perfluorohexane sulfonic acid (PFHxS), perfluoroheptanoic acid (PFHpA), perfluorononanoic acid (PFNA), and perfluorodecanic acid (PFDA) - and child behaviour (SDQ-total) and hyperactivity (sub-scale) at 5-9years of age in birth cohorts from Greenland and Ukraine. Pregnancy serum samples (N=1023) were analysed for perfluoroalkyl substances (PFASs) and categorized into tertiles and also used as continuous exposure variables. Problem behaviour and hyperactivity were assessed, using the Strength and Difficulties Questionnaire (SDQ) and categorized as normal/borderline and abnormal. Associations were analysed using multiple logistic and linear regression. High compared to low prenatal PFHxS exposure was associated with 1.16 (95% confidence interval (CI): 0.08; 2.25) point higher SDQ-total (more problem behaviour) in Greenland and 0.80 (CI: 0.06; 1.54) point higher SDQ-total in the combined analyses, whereas no association was present in Ukraine alone. One natural log-unit increase in prenatal PFNA exposure was associated with 0.90 (CI: 0.10; 1.71) points higher SDQ-total in Greenland and 0.72 (CI: 0.13; 1.31) points higher in the combined analysis and no association in Ukraine. Prenatal PFAS exposure was unrelated to problem behaviour (abnormal SDQ-total). In the combined analysis, odds ratio (OR) (CI) for hyperactivity was 1.8 (1.0; 3.2) for one natural log-unit increase in prenatal PFNA and 1.7 (1.0; 3.1) for one natural log-unit increase in prenatal PFDA exposure. Findings are compatible with weak effects on child behaviour of prenatal exposure to some PFASs although spurious results are not entirely unlikely. The associations were strongest in Greenland.

Polyfluorinated compounds (PFCs) are authorized for use as greaseproofing agents in food contact paper. As C8-PFCs (8-carbons) are known to accumulate in tissues, shorter-chain C6-PFCs (6-carbons) have replaced C8-PFCs in many food contact applications. However, the potential of C6-PFCs for human biopersistence has not been fully evaluated. For the first time, we provide internal exposure estimates to key metabolites of 6:2 fluorotelomer alcohol (6:2 FTOH), a monomeric component of C6-PFCs, to extend our understanding of exposure beyond estimates of external exposure. Pharmacokinetic data from published rat and human studies on 6:2 FTOH were used to estimate clearance and area under the curve (AUC) for its metabolites: 5:3 fluorotelomer carboxylic acid (5:3 A), perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA). Internal exposure to 5:3 A was the highest of evaluated metabolites across species and it had the slowest clearance. Additionally, 5:3 A clearance decreased with increasing 6:2 FTOH exposure. Our analysis provides insight into association of increased internal 5:3 A exposure with high biopersistence potential of 6:2 FTOH. Our results identify 5:3 A as an important biomarker of internal 6:2 FTOH exposure for use in biomonitoring studies, and are potentially useful for toxicological assessment of chronic dietary 6:2 FTOH exposure.

A novel boron-doped diamond (BDD) flow-through cell was used to evaluate the electrochemical oxidation of perfluoroalkyl acids (PFAAs) in landfill leachates. Six different leachates with a concentration of individual PFAAs in the range of 102 − 104 ng/L were treated. The performance of the flow-through cell was assessed and compared with synthetic solutions for the oxidation of two representative PFAAs: perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Subsequently, the effect of current density and the variability of leachates composition was investigated for the electrochemical oxidation of PFAAs in real landfill leachates. Non-detect levels and >90% degradation was reached for PFOS and PFOA after 2 h of treatment for all leachates tested. Decreasing trends for perfluoroheptanoic acid (PFHpA), perfluorohexanoic acid (PFHxA), and perfluorohexanesulphonic acid (PFHxS), and increasing trends for perfluoropentanoic (PFPeA), perfluorobutanoic (PFBA), and perfluorobutanesulphonic acid (PFBS) were observed. The total PFAAs removal ranged from −138.6 to 73.5%. Correlations between the composition of the leachates and PFAAs removal percentages were determined. Overall, the results show the potential of electrochemical oxidation to oxidize PFAAs present in high strength water such as landfill leachates.

To address the health and environmental concerns associated with perfluorocarboxylic acids, the assessment of cytotoxicity and bioaccumulation of perfluorocarboxylic acids is essential. This study investigated the effect of perfluorocarboxylic acids having various chain lengths on mouse melanoma B16 cells. The extent of cytotoxicity of perfluorohexanoic acid (C6), perfluoroheptanoic acid (C7), perfluorooctanoic acid (C8), perfluorononanoic acid (C9) and perfluorodecanoic acid (C10) within a concentration range of 0.25–1600 μg/ml was determined. Based on results, the viability of cells was 90% or higher in the presence of C6, C7, C8 at a concentration of up to 200 μg/ml, indicating that B16 cells are safe in the presence of C6, C7 and C8. On the other hand, moderate cytotoxicity was observed with C9 or C10, even at a relatively low concentration of 25 μg/ml. When cells were incubated in the presence of the same concentration (100 or 200 μg/ml) of perfluorocarboxylic acids, the number of live cells decreased as the perfluoroalkyl chain length increased suggesting that long-chained perfluorocarboxylic acids are more cytotoxic than short-chained perfluorocarboxylic acids. The correlation between cellular uptake and perfluoroalkyl chain length was also investigated. The presence of C6 in the cells was not detected probably because of poor uptake. On the other hand, the presence of C7–C10 in the cells was confirmed and quantified by LC ESI MS. Results showed that cellular uptake of long-chained perfluorocarboxylic acids were significantly higher than short-chained perfluorocarboxylic acids.

Little is known about factors influencing infant perfluorinated alkyl acid (PFAA) concentrations. Associations between serum PFAA concentrations in 2-4-month-old infants ( n = 101) and determinants were investigated by multiple linear regression and general linear model analysis. In exclusively breast-fed infants, maternal serum PFAA concentrations 3 weeks after delivery explained 13% (perfluoroundecanoic acid, PFUnDA) to 73% (perfluorohexanesulfonate, PFHxS) of infant PFAA concentration variation. Median infant/maternal ratios decreased with increasing PFAA carbon chain length from 2.8 for perfluoroheptanoic acid and perfluorooctanoic acid (PFOA) to 0.53 for PFUnDA and from 1.2 to 0.69 for PFHxS and perfluorooctanesulfonate (PFOS). Infant PFOA, perfluorononanoic acid (PFNA), and PFOS levels increased 0.7-1.2% per day of gestational age. Bottle-fed infants had mean concentrations of PFAAs 2 times lower than and a mean percentage of branched (%br) PFOS isomers 1.3 times higher than those of exclusively breast-fed infants. PFOA, PFNA, and PFHxS levels increased 8-11% per week of exclusive breast-feeding. Infants living in an area receiving PFAA-contaminated drinking water had 3-fold higher mean perfluorobutanesulfonate (PFBS) and PFHxS concentrations and higher mean %br PFHxS. Prenatal PFAA exposure and postnatal PFAA exposure significantly contribute to infant PFAA serum concentrations, depending on PFAA carbon chain length. Moderately PFBS- and PFHxS-contaminated drinking water is an important indirect exposure source.

A novel method has been developed to improve sampling system response times for nominally "sticky" molecules such as HNO3 and NH3. The method reported here makes use of active, continuous passivation, where the instrument interfaces are continuously exposed to 0.01-1 ppm of fluorinated acidic or basic surfactants. To reduce HNO3 response times, perfluoroheptanoic acid and perfluorobutanesulfonic acid vapors are evaluated as passivation species. 1H,1H-perfluorooctylamine is used to improve NH3 response times. The resulting time responses using the perfluoroalkanoic acids are on the order of 0.4-0.7 s for a 75% quantitative recovery of HNO3, and 1-5 s for 90% recovery. Similar response time improvements are seen in detection of NH3 using perfluorooctylamine (1 s for a 75% recovery, ∼ 2 s for 90% recovery). This generally applicable methodology significantly improves the capability of eddy covariance flux and real-time plume-based measurements of highly polar molecules that have historically been hampered by slow response times due to adsorption on sampling system surfaces. The utility of this approach is demonstrated by field measurements of HNO3 eddy covariance fluxes in a central U.S. prairie.

The relationship between the serum concentrations of perfluoroalkyl compounds (PFCs) and growth parameters was investigated in 2-year-old Korean children. The study included 361 children aged 2years (192 boys and 169 girls; 22-27months), born at term appropriate-for-gestational-age, who visited between 2012 and 2013. Growth parameters of height and weight, and serum samples were collected from 2-year-old children. Four PFCs (perfluorohexane sulfonic acid [PFHxS], perfluorooctane sulfonic acid [PFOS], perfluorooctanoic acid [PFOA], and perfluorononanoic acid [PFNA]), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), and perfluoroheptanoic acid (PFHpA) were detected in >99, 93.4, 89.8, and 74.2% of the serum samples, respectively. The duration of breastfeeding was positively associated with the serum concentrations of ln-transformed PFHxS, PFOS, PFHpA, PFOA, PFNA, PFDA, and PFUnDA (all P

The exposure to perfluorinated compounds (PFCs) through the diet for humans is of great concern. Among the diet, dairy products are in great demand. This paper reports the study on the levels of 9 perfluorinated acids and 2 fluorotelomer acids in milk, milk powder and yoghurt purchased from Chinese markets from 2008 to 2009. The analytes were quantitated by high performance liquid chromatography/electrospray tandem mass spectrometry (HPLC-ESI-MS/MS). In milk samples, perfluoroheptanoic acid (PFHpA) and perfluorononanoic acid (PFNA) were detected frequently, both in 68% of samples. In milk powder samples, perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and PFNA were the only detected PFCs and none of them was observed in more than 35% of samples. In yoghurt, PFOA was the most frequently detected compound, found in 69% of samples. None of fluorotelomer acids was observed in any samples. The mean concentrations of total PFCs were 178 pg/g (wet weight) in milk, 98 pg/g (dry weight) in milk powder and 42 pg/g in yoghurt (wet weight). It is notable that the data of this study indicate significant differences (P

Perfluoroalkyl compounds (PFCs) were determined in 2 L surface water samples collected in the Atlantic Ocean onboard the research vessels Maria S. Merian along the longitudinal gradient from Las Palmas (Spain) to St. Johns (Canada) (150 W to 52 degrees W) and Polarstem along the latitudinal gradient from the Bay of Biscay to the South Atlantic Ocean (46 degrees N to 26 degrees S) in spring and fall 2007, respectively. After filtration the dissolved and particulate phases were extracted separately, and PFC concentrations were determined using high-performance liquid chromatography interfaced to tandem mass spectrometry. No PFCs were detected in the particulate phase. This study provides the first concentration data of perfluorooctanesulfonamide (FOSA), perfluorohexanoic acid, and perfluoroheptanoic acid from the Atlantic Ocean. Results indicate that trans-Atlantic Ocean currents caused the decreasing concentration gradient from the Bay of Biscay to the South Atlantic Ocean and the concentration drop-off close to the Labrador Sea. Maximum concentrations were found for FOSA, perfluorooctanesulfonate, and perfluorooctanoic acid at 302, 291, and 229 pg L-1, respectively. However, the concentration of each single compound was usually in the tens of picograms per liter range. South of the equator only FOSA and below 4 degrees S no PFCs could be detected. Perfluoroalkyl compounds (PFCs) were determined in 2 L surface water samples collected in the Atlantic Ocean onboard the research vessels Maria S. Merian along the longitudinal gradient from Las Palmas (Spain) to St. Johns (Canada) (15° W to 52° W) and Polarstern along the latitudinal gradient from the Bay of Biscay to the South Atlantic Ocean (46° N to 26° S) in spring and fall 2007, respectively. After filtration the dissolved and particulate phases were extracted separately, and PFC concentrations were determined using high-performance liquid chromatography interfaced to tandem mass spectrometry. No PFCs were detected in the particulate phase. This study provides the first concentration data of perfluorooctanesulfonamide (FOSA), perfluorohexanoic acid, and perfluoroheptanoic acid from the Atlantic Ocean. Results indicate that trans-Atlantic Ocean currents caused the decreasing concentration gradient from the Bay of Biscay to the South Atlantic Ocean and the concentration drop-off close to the Labrador Sea. Maximum concentrations were found for FOSA, perfluorooctanesulfonate, and perfluorooctanoic acid at 302, 291, and 229 pg L−1, respectively. However, the concentration of each single compound was usually in the tens of picograms per liter range. South of the equator only FOSA and below 4° S no PFCs could be detected.

A modified LC-MS/MS method for large-scale screening of metabolic phenotypes was developed and validated. Twenty amino acids and 5 metabolically related compounds are measured within 4 min using multiple reaction monitoring (MRM) transitions selective for each compound. Separation with a short C18 column and rapid gradient using the ion-pairing reagent perfluoroheptanoic acid allows chromatographic resolution of the isomers Ile and Leu and improved chromatographic peak shapes for Lys, Arg, and His. MRM transitions were established with capability to distinguish isomers Leu from Ile and Thr from homoserine even when chromatographic resolution is incomplete. The reproducibility of the assay was tested by adding eight stable isotope-labeled amino acid standards (AA*) to extracts of Arabidopsis thaliana seeds. In intra- and interday assay comparisons, mean coefficients of variation of the peak area ratios of AA/AA* were less than 5% for all but Gly/Gly-D2-15N1. Recoveries of these eight amino acids ranged from 62 to 94% and suppression of signal by the matrix were 31-65%. Dilution of seed extracts reduced ion suppression for early-eluting amino acids but had minimal effects for those eluting later. The intra- and interday accuracies for these eight amino acids were 77-131 and 88-133% of nominal concentrations, respectively.

The first 19F, 13C single- and multi-bond 2D NMR correlations using fluorine detection methods are reported for a perfluorinated alkyl chain. These heteronuclear correlations are observed in perfluoroheptanoic acid and combined with 19F-decoupled 13C data and homonuclear 19F, 19F COSY to derive a full set of unequivocal 19F and 13C assignments.

In this study, 10 perfluorochemicals (PFCs) were measured in meat, meat products, and eggs, and in indoor dust, collected in China. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were the most frequently detected PFCs in these samples. Mean concentrations of PFOS and PFOA in foodstuffs were in the range of 0.05-1.99 ng/g fresh wt and 0.06-12.5 ng/g fresh wt, respectively. The mean concentrations of PFOA, perfluoroheptanoic acid (PFHpA), and PFOS in indoor dust were 205, 14.0, and 4.86 ng/g, dry wt, respectively. The estimated daily intake of PFOS and PFOA from meat, meat products and eggs (EDI(meateggs)) ranged from 6.00 to 9.64 ng/d and from 254 to 576 ng/d, respectively, when the values below the limit of quantitation (LOQ) were assigned as 0, and from 8.80 to 15.0 ng/d and from 255 to 577 ng/d, respectively, when the values below the LOQ were set at 1/2LOQ. The EDI(meateggs) of PFOS and PFOA increased with increasing family income. The estimated daily intake of PFOS and PFOA through inhalation of dust (EDI(dust)) ranged from 0.23 to 0.31 ng/d and from 9.68 to 13.4 ng/d, respectively. The daily intakes of PFOS and PFOA from the consumption of meat, meat products, and eggs, and from dust ingestion, as calculated from our samples in this study, were compared with estimated daily intake of PFCs reported from the concentrations in drinking water, fish and seafood from China. Our calculations indicate that dietary sources (EDI(dietary)) account for the overwhelming proportion of (99% for PFOS and 98% for PFOA) total daily intake (TDI) in adults. The analyzed foodstuffs (meat, meat products, and eggs) were not the major contributors to dietary exposure to PFOS, whereas, meat was the primary contributor to dietary exposure to PFOA.

The potency of the induction of hepatomegaly, peroxisomal beta-oxidation and microsomal 1-acylglycerophoshocholine (1-acyl-GPC) acyltransferase was compared among perfluorinated fatty acids (PFCAs) with 6-9 carbon chain length in the liver of male and female mice. All PFCAs examined induced hepatomegaly and peroxisomal beta-oxidation and the potency was in the order of perfluorononanonic acid (PFNA), perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHA) and perfluorohexanoic acid (PFHeA) when compared with the relative doses to induce the two parameters. Microsomal 1-acyl-GPC acyltransferase was induced by PFHA, PFOA and PFNA, as was peroxisomal beta-oxidation. No significant sex-related difference was observed in the induction of peroxisomal beta-oxidation by any PFCAs examined. PFNA and PFOA accumulated in the liver of both male and female mice in a dose-dependent manner. PFHA accumulated in the liver to a lesser extent; little PFHeA accumulated in the liver. Hepatic concentrations of PFNA, PFOA and PFHA were higher in male mice than those in female mice. One linear regression line was confirmed between the activities of peroxisomal beta-oxidation and hepatic concentrations of PFHeA, PFHA, PFOA and PFNA in male mice regardless of their carbon chain lengths, and the activities were saturable at the concentrations over approximately 500 nmol/g liver. Similar linear regression line was obtained between the two parameters in female mice. These results suggest (i) that the longer the perfluoroalkyl chain becomes, the more PFCA accumulates in the liver of both male and female mice, (ii) that the accumulated PFCAs induce hepatomegaly, peroxisomal beta-oxidation and microsomal 1-acyl-GPC acyltransferase, and (iii) that the difference observed in the accumulation of PFHA, PFOA and PFNA in the liver between male and female mice is not enough to produce obvious sex-related difference in the induction of peroxisomal beta-oxidation.

The potency to accumulate triglyceride (TG) was compared between perfluorinated fatty acids (PFCAs) with different carbon chain lengths in the liver of male and female rats and induction of peroxisomal beta-oxidation. In male rats, either perfluoroheptanoic acid (C7) or perfluorooctanoic acid (C8) had no effect, although perfluorononanonic acid (C9) and perfluorodecanoic acid (C10) markedly accumulated TG. In female rats, C7, C8, and C9 did not cause TG accumulation, whereas C10 caused TG accumulation at the same level as in male rats. TG accumulation induced by C9 was regulated by the level of testosterone in male rats. In contrast with TG accumulation, peroxisomal beta-oxidation was induced by C8, C9, and C10 in male rats and by C9 and C10 in female rats. Only a slight difference was observed in the induction by C9 between male and female rats. The induction of TG accumulation by these PFCAs occurred in a dose-dependent manner and significantly correlated with hepatic concentrations of PFCA regardless of their carbon chain length, as was observed with induction of peroxisomal beta-oxidation. There is, however, a striking difference in the hepatic concentration of PFCA required to cause induction of TG accumulation and that of peroxisomal beta-oxidation. The concentration of PFCA required to induce TG accumulation is much higher than that to induce peroxisomal beta-oxidation. These results strongly suggest that TG accumulation induced by PFCAs, as well as the induction of peroxisomal beta-oxidation, is dependent only on the number of PFCA molecules in hepatocytes, but is not due to the difference in their chemical structures, and that there is a marked difference in the PFCA threshold to cause distinct biological effects.

Haloacetic acids are disinfection byproducts of the chlorination of drinking water. This paper presents the analysis of all nine chloro and bromohaloacetic acids (HAA9) at the submicrogram per liter level by microextraction with detection by electrospray-mass spectrometry. The haloacetic acids are extracted from acidified water through a microscale liquid-liquid extraction. Perfluoroheptanoic acid is added to the extracts, and the haloacetic acids are detected with electrospray-mass spectrometry. Confidence in the selective quantification of the haloacetic acids is achieved by observing the stable association complexes that are formed between the haloacetic acids and perfluoroheptanoic acid. The method detection limits for the haloacetic acids are less than 1 microg L(-1), depending on the haloacetic acid. Standard addition is used to quantify the haloacetic acids in several water matrixes.

Spices have been used since ancient times. Although they have been employed mainly as flavoring and coloring agents, their role in food safety is of increasing concern. In this study, the usefulness of a modified QuEChERS method, based on the d-SPE, with micro-HPLC–MS/MS system for the determination of selected perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonates (PFSAs) in spices was addressed. The commonly used spices in Spain and Slovakia were investigated. The studies showed the presence of perfluorooctanoic acid in 19 spices of Spanish and Slovak origin, and it ranged from 0.11 ng g−1 for garlic to 0.67 ng g−1 for peppermint. The perfluorobutanoic acid was quantified in 10 Slovak spices (from 1.13 ng g−1 for allspice to 37.82 ng g−1 for star anise), whereas perfluorobutane sulfonate was identified only in 12 Spanish spices and it ranged from 0.24 ng g−1 for cinnamon to 1.01 ng g−1 for coriander. In contrast, perfluoroheptanoic acid was identified only in Slovak cardamom (1.94 ng g−1) and coriander (0.74 ng g−1). The average consumption of spices in Europe is approximately 0.5 g day−1, while in Asia and northern Africa, it is many times higher. Average content of PFASs in this evaluation has a value 4.67 ng g−1 giving 2.33 ng day−1 per person. This study showed that daily used spices may contribute to the overall contamination of food by perfluoroalkyl substances.

Perfluorinated compounds (PFCs) have been detected in many environmental matrices, biota, and nonoccupationally exposed populations in China recently. However, little is known about the distribution and levels of various PFCs in the general population living in areas where there is PFC exposure. In the present study, the levels and prevalence of ten target PFCs were determined in 227 serum samples from a population of nonoccupationally exposed individuals in Shenzhen, China. Results indicated that human exposure to PFCs was prevalent in Shenzhen. Perfluorooctanoate (PFOA) was the dominant PFC contaminant in the serum samples, with a median concentration of 6.72 ng/mL, followed by perfluorooctane sulfonate (PFOS) with a median concentration of 2.07 ng/mL. Other PFCs were detected at much lower concentrations, with median concentrations ranging from 0.02 to 0.87 ng/mL. Statistically, no significant (P>0.05) gender differences were observed for any of the PFCs. Significant (P